WO2008112087A1 - Cyanoacrylate compositions incorporating graphite platelets - Google Patents
Cyanoacrylate compositions incorporating graphite platelets Download PDFInfo
- Publication number
- WO2008112087A1 WO2008112087A1 PCT/US2008/002703 US2008002703W WO2008112087A1 WO 2008112087 A1 WO2008112087 A1 WO 2008112087A1 US 2008002703 W US2008002703 W US 2008002703W WO 2008112087 A1 WO2008112087 A1 WO 2008112087A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- composition
- cyanoacrylate
- graphite
- graphite platelet
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/30—Nitriles
- C08F22/32—Alpha-cyano-acrylic acid; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Definitions
- the present invention is directed to cyanoacrylate-based adhesive compositions which exhibit improved shear strength and peel strength.
- Cyanoacrylate compositions have long been known in the art as excellent adhesives.
- U.S. Patent No. 3,836,377 notes among the additional known thickeners polyvinyl ethers such as polyvinylmethyl ether.
- U.S. Patent No. 3,692,752 discloses thickened cyanoacrylate solutions containing certain polyether acrylates/methacrylates, acrylic/methacrylic esters of bis(hydroxyalkyl) phosponic acid derivates, and acrylic/methacrylic esters of tris(hydroxyalkyl) cyanuric acid derivatives.
- U.S. Patent No. 4,105,715 discloses a cyanoacrylate adhesive composition which incorporates powdered organic fillers such as polycarbonate, polyvinylidene fluoride, polyethylene, and acrylic block copolymer resins containing saturated elastomer segments.
- U.S. Patent No. 4,440,910 discloses a cyanoacrylate adhesive composition containing elastomeric polymers such as acrylic rubbers as fillers that exhibit substantially increased strength and toughness.
- U.S. Patent No. 4,560,723 discloses a cyanoacrylate adhesive composition containing a toughener such as a core-shell thermoplastic/rubber copolymer which is treated to remove impurities which cause premature polymerization of the cyanoacrylates and a compatible organic compound having one or more aryl groups to provide improved retention of peel strength and toughness.
- U.S. Patent No. 5,340,873 teaches a cyanoacrylate composition where a high molecular weight polyester polymer is added therein to provide improved impact resistance and toughness with good flexibility.
- U.S. Patent No. 6,822,052 discloses a cyanoacrylate adhesive composition wherein an elastomeric copolymer is added to the cyanoacrylate monomer to increase the toughness of the adhesive upon cure.
- U.S. Patent No. 6,833,196 discloses a cyanoacrylate adhesive composition including an acrylic monomer toughening agent that has reduced acid generation, enhanced toughness, and faster fixturing speeds.
- the present invention is directed to a cyanoacrylate adhesFve composition which includes, in addition to the cyanoacrylate component, a graphite component, such as a graphite platelet material.
- a graphite component such as a graphite platelet material.
- the addition of this graphite component provides a cyanoacrylate adhesive composition with enhanced physical properties, including improved shear and peel strength, fracture toughness and environmental resistance.
- the graphite component may be chosen from a host of graphite materials, desirably with a purity level of at least about 95% carbon graphite, including standard purity graphite with a carbon level of about 97%, high purity graphite with a carbon level of about 99%, or combinations thereof.
- the present invention is directed to a method of bonding two or more substrates including the steps of providing at least two substrates; applying, onto at least a portion of a surface of one or both of the at least two substrates, a cyanoacrylate composition incorporating a graphite component; contacting the surfaces of the at least two substrates having the cyanoacrylate composition therebetween; and curing the cyanoacrylate composition.
- the present invention is directed to a bonded assembly including: a first substrate having a first surface; another substrate having a second surface; and a cured cyanoacrylate composition disposed between the first and second surfaces, the composition having included prior to cure: a cyanoacrylate component and the graphite component as noted above.
- the present invention is directed to a method of increasing the peel strength, block shear, fracture toughness and environmental resistance by incorporating a graphite platelet component into the composition, followed by curing of the composition.
- the present invention involves a strengthened cyanoacrylate composition, which : includes, beyond the cyanoacrylate component, a graphite component. Depending on the nature of the graphite component, toughness is imparted to the composition.
- the cyanoacrylate compositions of the present invention include a cyanoacrylate component which includes at least one cyanoacrylate monomer.
- the cyanoacrylate is desirably an ⁇ -cyanoacrylate ester, such as those represented by the following structure:
- R 1 represents a straight chain or branched chain alkyl group having 1 to 12 carbon atoms (which may be substituted with a substituent such as a halogen atom or an alkoxy group), a straight chain or branched chain alkenyl group having 2 to 12 carbon atoms, a straight chain or branched chain alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group, an aralkyl group or any aryl group.
- R 1 are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an allyl group, a methallyl group, a crotyl group, a propargyl group, a cyclohexyl group, a benzyl group, a phenyl group, a cresyl group, a 2-choroethyl group, a 3-choropropyl group, a 2-chorobutyl group, a trifluoroethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group and a 2-ethoxyethyl group.
- Ethyl cyanoacrylate is a particularly desirable choice for use in the inventive compositions.
- a single ⁇ -cyanoacrylate monomer or a mixture of two or more of these ⁇ - cyanoacrylate monomers can be used.
- the above ⁇ -cyanoacrylate monomer is used alone as an adhesive, and one or more components such as those set forth below, are used to formulate a commercial composition.
- the additional components include, but are not limited to, accelerators; anionic polymerization inhibitors; radical polymerization inhibitors; additives, such as plasticizers, heat stabilizers and toughening agents; fillers; and/or perfumes, dyes, and pigments. The use of these additives is well known to those skilled in the art.
- a suitable amount of cyanoacrylate monomer present in the inventive compositions is from about 50 to about 99% by weight, such as 60 to 90% by weight, desirably 85% by weight to about 98% by weight, based on the total weight of the composition.
- compositions of the present invention exhibit enhanced toughness due to the inclusion of a graphite component, which provides for enhanced toughening properties when compared with corresponding compositions which do not include such a graphite component.
- the graphite component used in accordance with this invention may represent a graphite platelet structure. More particularly, the graphite is derived from mined graphite which is treated and processed so as to alter the physical structure of the graphite to form a graphite platelet structure, having specific characteristics and dimensions. For example, mined graphite may be impregnated with an acid and sent through a furnace where the acid rapidly volatizes and exfoliates the graphite. Such a process is taught, for example, in U.S. Patent No. 6,129,972, the disclosure of which is hereby expressly incorporated herein by reference. The exfoliated graphite may then be subjected to mechanical processing, such as jet milling.
- the graphite component prepared through such processing, and useful in accordance with the present invention exhibits a morphology of flakes and platelets in various shapes and sizes, having length and width dimensions generally on the order of about 1 micrometer ( ⁇ m) to about 100 ⁇ m, particularly from about 2 ⁇ m to about 50 ⁇ m, such as from about 5 ⁇ m to about 20 ⁇ m, and having an average platelet thickness of less than 1 ⁇ m, particularly from about 0.1 to about 0.9 ⁇ m (i.e., ranging in the hundreds of nanometers).
- Such graphite platelets are distinguished from graphite particles or graphite fibers, which have morphology distinct from such graphite platelets.
- particles have one characteristic dimension, diameter, resulting in aspect ratios of 1 and low degrees of reinforcement per loading level.
- Fibers have two characteristic dimensions, diameter and length, whose quotient defines the aspect ratio of the fiber and hence the relative efficiency of reinforcement.
- Platelets have three characteristic dimensions, length, width and thickness, where the ratio of the two aspect ratios (w/t and l/t) is close to unity and they have the specific advantage of maximum reinforcement at low loadings.
- the graphite platelets desirably exhibit a purity level of at least about 95% carbon, desirably about 97% carbon, and more desirably about 99% carbon.
- Such high levels of purity may be obtained by optionally subjecting the graphite platelets to a purification treatment subsequent to the exfoliation and milling treatment in order to further purify the graphite, thereby achieving a high level of carbon content and eliminating any residual acid from the graphite platelet structure.
- Examples of commercially available graphite platelet materials useful in accordance with the present invention include products available from Graftech International Ltd. (Cleveland, OH), under the product number TG-679, representing a standard purity graphite platelets having a purity of about 97% carbon; and TG-684HP, 407 A, and 407B, representing high purity graphite platelets having a purity of about 99% carbon. Such materials are believed to be prepared in accordance with an acid exfoliation treatment such as that noted above, and desirably include no residual acid in the final graphite platelet product.
- the graphite component is included within the composition in an amount within the range of from about 0.1% by weight to about 5.0% by weight based on the total weight of the composition. Desirably, the graphite component is included in an amount between about 0.1% by weight and 2.0% by weight based on the total weight of the composition, and more desirably, in an amount of about 1.0% by weight based on the total weight of the composition.
- An anionic polymerization inhibitor is generally added to ⁇ -cyanoacrylate compositions to increase the stability of the composition during storage.
- the cyanoacrylate monomers are preferably stabilized using acid stabilizers of the Lewis or protonic types.
- acid stabilizers include nitric oxide (NO), sulfur dioxide (SO 2 ), sulfur trioxide (SO3), boron trifluoride (BF ⁇ ), hydrogen fluoride (HF), methane sulfonic acid (MSA), organic sultone inhibitors, aromatic sulfonic acids, aliphatic sulfonic acids, sulfones and mixtures and combinations thereof.
- a stabilizer system for the present invention includes MSA and SO 2 , for example, with MSA in an amount from about 5 to about 30 ppm and SO 2 in an amount of from about 2 to about 30 ppm based on the amount of the cyanoacrylate monomer.
- BF 3 may be added in amounts of about 5 ppm to about 50 ppm based on the amount of the cyanoacrylate monomer.
- such small amounts of stabilizers used with the composition of the present invention provide optimal performance without stability concerns.
- a radical polymerization inhibitor may be added to the cyanoacrylate compositions as well, in an amount from about 0.001 to 2.0%, particularly 0.03 to 0.5%, based on the total weight of the composition, for the purpose of capturing radicals which are formed by light during storage.
- Such inhibitors are ordinarily of the phenolic type including, for example, hydroquinone and hydroquinone monomethyl ether.
- Other inhibitors suitable for use herein include butylated hydroxytoluene and butylated hydroxyanisole.
- a thickener may be added to increase the viscosity of the cyanoacrylate composition; however, the graphite platelet material may exhibit a thickening effect to the composition, and therefore a thickener may not be desirable, particularly depending on the amount of graphite platelet material incorporated into the composition. Viscosities of 10,000 cps or greater are desirable to achieve dispersions of cyanoacrylate compositions with shelf life stability.
- various materials can be useful as thickeners, and examples include poly(methyl methacrylate) (PMMA), methacrylate-type copolymers, acrylic rubbers, cellulose derivatives, polyvinyl acetate and poly( ⁇ -cyanoacrylate).
- a suitable amount of thickener is generally about 0.01% to about 30% by weight, desirably about 5.0% to about 25% by weight, such as about 5.0% to about 10% based on the total weight of the composition.
- Compositions with particularly desirable physical properties may be obtained where less than 10% PMMA thickener is used and in the absence of silica type thickeners.
- the cyanoacrylate composition of the present invention may further include one or more rubber tougheners.
- rubber tougheners such as those disclosed in U.S. Patent No. 4,440,910 to O'Connor, which discloses certain organic polymers as toughening additives that are elastomeric, (i.e., rubbery) in nature, may be incorporated into the composition.
- elastomeric polymers may be selected from, for example, copolymers of a lower alkene monomer and (i) acrylic acid esters, (ii) methacrylic acid esters or (iii) vinyl acetate.
- the toughening additives may be one or more acrylic rubbers; polyester resins; ethylene-vinyl acetates; fluorinated rubbers; isoprene-acrylonitrile polymers; chlorosulfonated poyethylenes; and/or homopolymers of polyvinyl acetate.
- the elastomeric polymers may be selected from homopolymers of alkyl esters of acrylic acid; copolymers of another polymerizable monomer, such as lower alkenes, with an alkyl or alkoxy ester of acrylic acid; and copolymers of alkyl or alkoxy esters of acrylic acid.
- elastomeric polymers useful in the compositions of the present invention is copolymers of methyl acrylate and ethylene, manufactured by DuPont, under the name of VAMAC, such as VAMAC N 123 and VAMAC B-124.
- VAMAC N 123 and VAMAC B-124 are reported by DuPont to be a master batch of ethylene/acrylic elastomer.
- Henkel Corporation (as the successor to Loctite Corporation) has sold for a number of years since the filing of the '910 patent rubber toughened cyanoacrylate adhesive products under the trade name BLACK MAX, which employ as the rubber toughening component the DuPont materials called VAMAC B-124 and N 123. Thus, these DuPont materials may be used to co-toughen the inventive composition.
- Henkel has sold in the past clear and substantially colorless rubber toughened cyanoacrylate adhesive products, namely, LOCTITE 4203, 4204, 4205 and 435, which employ as the rubber toughening component the DuPont material, VAMAC G and VAMAC MR.
- VAMAC G and VAMAC MR may be used to co-toughen the inventive composition, as well.
- VAMAC VCS rubber appears to be the base rubber, from which the remaining members of the VAMAC product line are compounded.
- VAMAC VCS is a reaction product of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, which once formed is then substantially free of processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine.
- processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine.
- DuPont has provided to the market under the trade designation
- VAMAC VMX 1012 and VCD 6200 which are rubbers made from ethylene and methyl acrylate. It is believed that the VAMAC VMX 1012 rubber possesses little to no carboxylic acid in the polymer backbone. Like the VAMAC VCS rubber, the VAMAC VMX 1012 and VCD 6200 rubbers are substantially free of processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine, noted above.
- processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine, noted above.
- the inventive composition may also be co-toughened with a rubber toughening component having (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), which once the reaction products and/or dipolymers are formed are then substantially free of processing aids, such as the release agents octadecyl amine (reported by Du Pont to be available commercially from Akzo Nobel under the tradename ARMEEN 18D), complex organic phosphate esters (reported by DuPont to be available commercially from RT. Vanderbilt Co., Inc.
- a rubber toughening component having (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), which once the reaction products and/or dipolymers are formed are then substantially
- VANFRE VAM stearic acid and/or polyethylene glycol ether wax
- anti-oxidants such as substituted diphenyl amine (reported by DuPont to be available commercially from Uniroyal Chemical under the tradename NAUGARD 445).
- Commercial examples of such rubber tougheners include VAMAC MR, VMX 1012 and VCD 6200 rubbers, and these may be used too.
- Phthalic anhydride and other plasticizers may also be added to the cyanoacrylate component to further aid in durability and impact, heat and moisture resistance.
- the plasticizer is preferably present in an amount of about 0.005% to about 5.0%, desirably about 0.01% to about 2.0% by weight based on the total weight of the composition.
- Perfumes, dyes, pigments and the like may be added to the inventive composition depending on use purposed in amounts which do not adversely affect the stability of the cyanoacrylate monomer. The use of such additives is within the skill of those practicing in the cyanoacrylate adhesive art and need not be detailed herein.
- Accelerators that may be useful in the cyanoacrylate compositions include for example calixarenes, oxacalixarenes, and combinations thereof. Of the calixarenes and oxacalixarenes, many are known, and are reported in the patent literature. See U.S. Patent Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461 , the disclosures of each of which are hereby expressly incorporated herein by reference.
- crown ether Another potentially useful accelerator component is crown ether.
- a host of crown ethers are known.
- examples which may be used herein either individually or in combination, or in combination with the calixarenes and oxacalixarenes described above include: 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15- crown-5, dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym- dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24- crown-8, cyclohexyl-12-crown-4, 1 ,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown-5, 1 ,2-methyl-benzo-18-crown-6, 1 ,2-methylbenz
- R 3 and R 4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer
- R 5 is H or CH 3 and n is an integer of between 1 and 4.
- suitable R 3 and R 4 groups are R groups, alkoxy groups such as methoxy, and aryloxy groups such as phenoxy.
- the R 3 and R 4 groups may contain halogen or other substituents, an example being trifluoropropyl.
- groups not suitable as R 4 and R 5 groups are basic groups such as amino, substituted amino and alkylamino.
- the accelerator component may be included in the compositions in an amount within the range of from about 0.1% to about 10%, with the range of about 0.5% to about 5% being desirable. See U.S. Patent Nos. 4,170,585; 4,450,265; 6,294,629; and 6,475,331, the contents of which are all incorporated herein by reference.
- the cyanoacrylate compositions of the present invention are easily prepared by adding predetermined amounts of the graphite component to the cyanoacrylate component and conducting stirring for a sufficient time and temperature to achieve a homogenous solution or suspension.
- the graphite component provides the composition with a uniformly dispersed metallic grayish-black color. As such, the graphite component acts as a pigment for the cyanoacrylate composition, thereby eliminating the need for further pigments or colorants, particularly where gray adhesive compositions are desired.
- the graphite component represents a high level of pure carbon, with greater than 95% carbon purity. When this graphite component is combined with the cyanoacrylate monomer, the high levels of carbon impart a distinct color to the composition, exhibiting a very dark grey to black color.
- the cyanoacrylate compositions of the present invention are useful in bonding two or more substrates. A sufficient portion of the composition may be placed on a surface of one of the two or more substrates. The other substrate is then positioned over the cyanoacrylate composition and the two substrates contacted together to form an assembly. The assembly is then exposed to favorable cure conditions to cure the cyanoacrylate composition.
- compositions of the present invention exhibit enhanced physical properties, such as improved strength, fracture toughness and environmental resistance of the compositions when cured. Such enhancements are manifested through various physical properties, such as 180° peel strength and tensile and block shear strength, which are indicative of useful bond strengths.
- compositions in accordance with the present invention may exhibit improvements in peel strength on the order of more than a 50% increase in peel strength when compared with compositions which do not include any graphite component, even at graphite load levels as low as 0.1%.
- Graphite load levels of about 1% are desirable, and provide improved peel strength of more than 400% when compared with compositions which do not include any graphite component.
- With toughened cyanoacrylate compositions including rubber modifiers improvements in peel strength on the order of more than a 35% increase may be exhibited when compared with compositions which do not include any graphite component, particularly with graphite load levels of about 1%.
- Improvements in block shear strength on the order of increases of more than 40% when compared with compositions which do not include any graphite component may be exhibited, particularly with graphite load levels of about 1 %.
- Significant increases in fracture toughness may also be exhibited, on the order of greater than 100% increase in fracture toughness when compared with compositions which do not include any graphite component, particularly with graphite load levels of about 1%.
- improvements in environmental resistance may be exhibited on the order of an increase in lap shear strength of more than 20% after exposure to environmental aging conditions, when compared with compositions which do not include any graphite component, particularly with graphite load levels of about 1%.
- Cyanoacrylate compositions identified as Samples 1-13 were prepared by incorporating varying amounts of graphite platelet materials into cyanoacrylate compositions, as set forth in Table 1.
- compositions were prepared by adding the indicated amount of graphite platelet material to the identified cyanoacrylate component, with mild heating if necessary, with the composition stirred until the graphite platelet material was homogenously dispersed within the composition.
- Stabilized ethyl cyanoacrylate based one-part adhesive composition commercially available as LOCTITE 401 from Henkel Corporation, Rocky Hill, CT.
- Toughened ethyl cyanoacrylate based one-part adhesive composition incorporating rubber modifiers commercially available as LOCTITE 435 from Henkel Corporation, Rocky Hill, CT.
- Samples 1-13 were tested for peel strength in accordance with procedures of the American Standard Test Methods (ASTM) No. D-903, the test method incorporated herein by reference.
- the substrates used for determining peel strength included grit blasted steel bonded to grit blasted flexible steel shims.
- the grit used to prepare the specimens was 80 mesh silicon carbide (SiC).
- the peel strength measurements for each of Samples 1-13 were compared with peel strength measurements for comparison cyanoacrylate compositions which included the cyanoacrylate component of Table 1 but without the graphite platelet components set forth in Table 1.
- cyanoacrylate compositions incorporating graphite platelet materials therein was measured.
- cyanoacrylate compositions were prepared as Samples 14 and 15 by incorporating 0.1 and 1%, respectively, of high purity graphite platelets ( ⁇ 99% carbon content, available as TG-684HP from Graftech Industries, Ltd., Cleveland, OH) into a cyanoacrylate adhesive composition, LOCTITE 435, commercially available from Henkel Corporation, Rocky Hill, CT.
- the compositions of Samples 14 and 15 were prepared by adding the indicated amount of graphite platelet material to the cyanoacrylate component, with stirring and under mild heating conditions until the graphite platelet material was homogenously dispersed within the composition.
- compositions thus prepared were tested for tensile shear strength, in accordance with ASTM No. D-1002, the test method incorporated herein by reference.
- Tensile shear strength was determined using grit blasted mild steel lap shears bonded to each other and pulled in tension to failure after 0.5, 3, 6, 24, and 72 hours of cure at ambient conditions.
- Tensile shear strength measurements for each of Samples 14 and 15 were compared with tensile shear strength measurements for LOCTITE 435 without the graphite platelet components set forth in Table 1.
- a cyanoacrylate composition was prepared as Sample 16 by incorporating 1 % of standard purity graphite platelets ( ⁇ 97% carbon content, available as TG-679 from Graftech Industries, Ltd., Cleveland, OH) into a cyanoacrylate adhesive composition, LOCTITE 435, commercially available from Henkel Corporation, Rocky Hill, CT.
- the composition of Sample 16 was prepared by adding the indicated amount of graphite platelet material to the cyanoacrylate component, with mild heating if necessary, stirring and under mild heating conditions until the graphite platelet material was homogenously dispersed within the composition.
- the composition of Sample 16 was applied between various substrates, including polycarbonate and polyvinyl chloride, and tested for block shear strength in accordance with ASTM No. D-4501 , the test method incorporated herein by reference.
- a cyanoacrylate composition was prepared as Sample 17 by incorporating 1% of standard purity graphite platelets (-97% carbon content, available as TG-679 from Graftech Industries, Ltd., Cleveland, OH) into a cyanoacrylate adhesive composition, LOCTITE 411 , commercially available from Henkel Corporation, Rocky Hill, CT.
- the composition of Sample 17 was prepared by adding the indicated amount of graphite platelet material to the cyanoacrylate component, with stirring and under mild heating conditions until the graphite platelet material was homogenously dispersed within the composition.
- Sample 17 was applied between chromic acid etched 7075 aluminum and tested for fracture toughness in accordance with ASTM Standard D-3433, the testing protocol incorporated herein by reference.
- the testing involved an aluminum double cantilever beam, at 0 mil induced bond gap.
- EXAMPLE 5 The environmental resistance for certain polymeric materials was tested as follows. Cyanoacrylate compositions were prepared as Samples 18 and 19 by incorporating 1% of standard purity graphite platelets ( ⁇ 97% carbon content, available as TG-679 from Graftech Industries, Ltd., Cleveland, OH) and 1% of high purity graphite platelets (-99% carbon content, available as TG-684HP from Graftech Industries, Ltd., Cleveland, OH), respectively, into a cyanoacrylate adhesive composition, LOCTITE 401 , commercially available from Henkel Corporation, Rocky Hill, CT.
- LOCTITE 401 commercially available from Henkel Corporation, Rocky Hill, CT.
- compositions of Samples 18 and 19 were prepared by adding the indicated amount of graphite platelet material to the cyanoacrylate component, with mild heating if necessary, with the composition stirred until the graphite platelet material was homogenously dispersed within the composition.
- the compositions of Samples 18 and 19 were applied between grit blasted mild steel lap shears, exposed to accelerated environmental aging condition of 4O 0 C with 95% relative humidity for 500 hours, and tested for lap shear strength in accordance with ASTM No. D-1002, the test method incorporated herein by reference.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009552699A JP2010520935A (en) | 2007-03-09 | 2008-02-29 | Cyanoacrylate composition including graphite platelets |
DE602008006369T DE602008006369D1 (en) | 2007-03-09 | 2008-02-29 | CYANACRYLATE COMPOSITIONS WITH GRAPHITE PLATES |
CA002680574A CA2680574A1 (en) | 2007-03-09 | 2008-02-29 | Cyanoacrylate compositions incorporating graphite platelets |
MX2009009639A MX2009009639A (en) | 2007-03-09 | 2008-02-29 | Cyanoacrylate compositions incorporating graphite platelets. |
AT08726274T ATE506412T1 (en) | 2007-03-09 | 2008-02-29 | CYANACRYLATE COMPOSITIONS WITH GRAPHITE PLATES |
EP08726274A EP2121777B1 (en) | 2007-03-09 | 2008-02-29 | Cyanoacrylate compositions incorporating graphite platelets |
BRPI0808436-0A BRPI0808436A2 (en) | 2007-03-09 | 2008-02-29 | METHOD FOR IMPROVING HIGHLIGHTING RESISTANCE OF A RUBBER-TYPICAL CYANOCACRILATE COMPOSITION, AND TWO OR MORE SUBSTRATE CONNECTION METHOD. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68426707A | 2007-03-09 | 2007-03-09 | |
US11/684,267 | 2007-03-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008112087A1 true WO2008112087A1 (en) | 2008-09-18 |
Family
ID=39759805
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2008/002703 WO2008112087A1 (en) | 2007-03-09 | 2008-02-29 | Cyanoacrylate compositions incorporating graphite platelets |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP2121777B1 (en) |
JP (1) | JP2010520935A (en) |
KR (1) | KR20100015428A (en) |
CN (1) | CN101663338A (en) |
AT (1) | ATE506412T1 (en) |
BR (1) | BRPI0808436A2 (en) |
CA (1) | CA2680574A1 (en) |
DE (1) | DE602008006369D1 (en) |
ES (1) | ES2360486T3 (en) |
MX (1) | MX2009009639A (en) |
PT (1) | PT2121777E (en) |
WO (1) | WO2008112087A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8456586B2 (en) | 2009-06-11 | 2013-06-04 | Apple Inc. | Portable computer display structures |
WO2015059644A1 (en) | 2013-10-24 | 2015-04-30 | Afinitica Technologies, S. L. | Cyanoacrylate composition |
US12043772B2 (en) | 2019-06-12 | 2024-07-23 | Henkel Ag & Co. Kgaa | Graphene oxide modified two-part cyanoacrylate/free radically curable adhesive systems |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103131335B (en) * | 2011-11-28 | 2015-04-01 | 宝山钢铁股份有限公司 | Preparation dedicated binder of microbeam analysis standard sample and blending method thereof |
WO2013174431A1 (en) * | 2012-05-23 | 2013-11-28 | Henkel Ag & Co. Kgaa | A curable composition comprising cyanoacrylate monomers |
WO2013174430A1 (en) * | 2012-05-23 | 2013-11-28 | Henkel Ag & Co. Kgaa | An article comprising a film on a carrier or release substrate |
CN103031012B (en) * | 2012-12-14 | 2016-06-15 | 长沙岱勒新材料科技股份有限公司 | A kind of compositions and the method for preparing diamond fretsaw thereof |
CN103275625A (en) * | 2013-05-28 | 2013-09-04 | 浙江凌志精细化工有限公司 | Adhesive for quickly mutually sticking vulcanized silicone rubbers and preparation method of adhesive |
JP6241375B2 (en) * | 2014-06-30 | 2017-12-06 | 東亞合成株式会社 | Colored 2-cyanoacrylate adhesive composition |
CN105527117A (en) * | 2015-12-02 | 2016-04-27 | 成都理工大学 | Field in-situ sampling method for granular mixtures |
CN106519995A (en) * | 2016-10-26 | 2017-03-22 | 三友(天津)高分子技术有限公司 | Toughened alpha-cyanoacrylate adhesive |
GB2567219B (en) | 2017-10-06 | 2021-08-11 | Henkel IP & Holding GmbH | Thermoplastic polyurethane toughened cyanoacrylate compositions |
CN113679876B (en) * | 2021-08-13 | 2022-08-12 | 上海恩盛医疗科技有限公司 | Medical soft tissue adhesive and preparation method thereof |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4170585A (en) | 1977-08-05 | 1979-10-09 | Toagosei Chemical Industry Co., Ltd. | Adhesive composition |
US4450265A (en) | 1980-08-28 | 1984-05-22 | Loctite Corporation | Additives for cyanoacrylate adhesives |
US4526636A (en) * | 1984-05-29 | 1985-07-02 | Mader Gerald J | Method of repairing breaks in sheet material |
US4556700A (en) | 1984-01-30 | 1985-12-03 | Loctite Limited | Instant adhesive composition utilizing calixarene accelerators |
US4622414A (en) | 1984-01-27 | 1986-11-11 | Loctite Limited | Novel calixarene compounds |
US4636539A (en) | 1984-01-30 | 1987-01-13 | Loctite (Ireland) Limited | Instant adhesive composition utilizing calixarene accelerators |
US4646765A (en) * | 1986-02-03 | 1987-03-03 | Cooper Donald E | Nail compositions containing cyanoacrylate and graphite |
US4695615A (en) | 1984-11-21 | 1987-09-22 | Loctite (Ireland) Limited | Instant adhesive composition utilizing mixed functionality calixarenes as accelerators |
US4718966A (en) | 1984-01-30 | 1988-01-12 | Loctite (Ireland) Ltd. | Bonding method utilizing cyanoacrylate adhesive having calixarene accelerator |
US4837260A (en) | 1986-05-23 | 1989-06-06 | Toagosei Chemical Industry Co., Ltd. | Cyanoacrylate compositions |
US4855461A (en) | 1987-01-21 | 1989-08-08 | Loctite (Ireland) Ltd. | Functionalized oxacalixarenes, their preparation and use in instant adhesive compositions |
US4906317A (en) | 1983-11-10 | 1990-03-06 | Loctite Corporation | Instant adhesive composition and bonding method employing same |
US4946892A (en) * | 1987-10-05 | 1990-08-07 | Ucar Carbon Technology Corporation | Composites of in-situ exfoliated graphite |
US5312864A (en) | 1990-03-26 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | α-cyanoacrylate adhesive compositions |
US6129972A (en) | 1997-09-18 | 2000-10-10 | The Procter & Gamble Company | Embossed joined laminae having an essentially continuous network and juxtaposed embossments |
US6294629B1 (en) | 1998-11-23 | 2001-09-25 | Loctite (R&D) Limited | Cyanoacrylate compositions |
JP2001270041A (en) * | 2000-03-23 | 2001-10-02 | Spirulina Biological Lab Ltd | Method for manufacturing composite material |
US6475331B1 (en) | 2001-06-26 | 2002-11-05 | Henkel Loctite Corporation | Cyanoacrylate compositions |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4440910A (en) * | 1982-01-18 | 1984-04-03 | Loctite Corporation | Toughened cyanoacrylates containing elastomeric rubbers |
US4980086A (en) * | 1985-10-16 | 1990-12-25 | Toagosei Chemical Industry, Co., Ltd. | Curable composition |
-
2008
- 2008-02-29 ES ES08726274T patent/ES2360486T3/en active Active
- 2008-02-29 DE DE602008006369T patent/DE602008006369D1/en active Active
- 2008-02-29 PT PT08726274T patent/PT2121777E/en unknown
- 2008-02-29 KR KR1020097020994A patent/KR20100015428A/en not_active Application Discontinuation
- 2008-02-29 CA CA002680574A patent/CA2680574A1/en not_active Abandoned
- 2008-02-29 AT AT08726274T patent/ATE506412T1/en not_active IP Right Cessation
- 2008-02-29 CN CN200880012773A patent/CN101663338A/en active Pending
- 2008-02-29 WO PCT/US2008/002703 patent/WO2008112087A1/en active Application Filing
- 2008-02-29 MX MX2009009639A patent/MX2009009639A/en unknown
- 2008-02-29 BR BRPI0808436-0A patent/BRPI0808436A2/en not_active IP Right Cessation
- 2008-02-29 JP JP2009552699A patent/JP2010520935A/en active Pending
- 2008-02-29 EP EP08726274A patent/EP2121777B1/en not_active Not-in-force
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4170585A (en) | 1977-08-05 | 1979-10-09 | Toagosei Chemical Industry Co., Ltd. | Adhesive composition |
US4450265A (en) | 1980-08-28 | 1984-05-22 | Loctite Corporation | Additives for cyanoacrylate adhesives |
US4906317A (en) | 1983-11-10 | 1990-03-06 | Loctite Corporation | Instant adhesive composition and bonding method employing same |
US4622414A (en) | 1984-01-27 | 1986-11-11 | Loctite Limited | Novel calixarene compounds |
US4718966A (en) | 1984-01-30 | 1988-01-12 | Loctite (Ireland) Ltd. | Bonding method utilizing cyanoacrylate adhesive having calixarene accelerator |
US4556700A (en) | 1984-01-30 | 1985-12-03 | Loctite Limited | Instant adhesive composition utilizing calixarene accelerators |
US4636539A (en) | 1984-01-30 | 1987-01-13 | Loctite (Ireland) Limited | Instant adhesive composition utilizing calixarene accelerators |
US4526636A (en) * | 1984-05-29 | 1985-07-02 | Mader Gerald J | Method of repairing breaks in sheet material |
US4695615A (en) | 1984-11-21 | 1987-09-22 | Loctite (Ireland) Limited | Instant adhesive composition utilizing mixed functionality calixarenes as accelerators |
US4646765A (en) * | 1986-02-03 | 1987-03-03 | Cooper Donald E | Nail compositions containing cyanoacrylate and graphite |
US4837260A (en) | 1986-05-23 | 1989-06-06 | Toagosei Chemical Industry Co., Ltd. | Cyanoacrylate compositions |
US4855461A (en) | 1987-01-21 | 1989-08-08 | Loctite (Ireland) Ltd. | Functionalized oxacalixarenes, their preparation and use in instant adhesive compositions |
US4946892A (en) * | 1987-10-05 | 1990-08-07 | Ucar Carbon Technology Corporation | Composites of in-situ exfoliated graphite |
US5312864A (en) | 1990-03-26 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | α-cyanoacrylate adhesive compositions |
US6129972A (en) | 1997-09-18 | 2000-10-10 | The Procter & Gamble Company | Embossed joined laminae having an essentially continuous network and juxtaposed embossments |
US6294629B1 (en) | 1998-11-23 | 2001-09-25 | Loctite (R&D) Limited | Cyanoacrylate compositions |
JP2001270041A (en) * | 2000-03-23 | 2001-10-02 | Spirulina Biological Lab Ltd | Method for manufacturing composite material |
US6475331B1 (en) | 2001-06-26 | 2002-11-05 | Henkel Loctite Corporation | Cyanoacrylate compositions |
Non-Patent Citations (1)
Title |
---|
CHORBADZHIEV K. ET AL.: "The effect of fillers upon the properties of electroconductive cyanoacrylate adhesives", INTERNATIONAL JOURNAL OF ADHESION AND ADHESIVES, vol. 8, no. 3, pages 143 - 146, XP008112179 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8456586B2 (en) | 2009-06-11 | 2013-06-04 | Apple Inc. | Portable computer display structures |
WO2015059644A1 (en) | 2013-10-24 | 2015-04-30 | Afinitica Technologies, S. L. | Cyanoacrylate composition |
US10144851B2 (en) | 2013-10-24 | 2018-12-04 | Afinitica Technologies, S. L. | Cyanoacrylate composition |
US12043772B2 (en) | 2019-06-12 | 2024-07-23 | Henkel Ag & Co. Kgaa | Graphene oxide modified two-part cyanoacrylate/free radically curable adhesive systems |
Also Published As
Publication number | Publication date |
---|---|
ATE506412T1 (en) | 2011-05-15 |
EP2121777A1 (en) | 2009-11-25 |
EP2121777B1 (en) | 2011-04-20 |
CA2680574A1 (en) | 2008-09-18 |
BRPI0808436A2 (en) | 2014-07-29 |
JP2010520935A (en) | 2010-06-17 |
DE602008006369D1 (en) | 2011-06-01 |
PT2121777E (en) | 2011-05-25 |
MX2009009639A (en) | 2010-01-15 |
ES2360486T3 (en) | 2011-06-06 |
EP2121777A4 (en) | 2010-03-17 |
CN101663338A (en) | 2010-03-03 |
KR20100015428A (en) | 2010-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2121777B1 (en) | Cyanoacrylate compositions incorporating graphite platelets | |
AU2006268160B2 (en) | Toughened cyanoacrylate compositions | |
CN109476874B (en) | Two-part cyanoacrylate curable adhesive systems | |
JP6794460B2 (en) | Cyanoacrylate composition | |
US10947418B2 (en) | Cyanoacrylate compositions | |
WO2010029134A1 (en) | Toughened cyanoacrylate compositions | |
US8287687B1 (en) | Cyanoacrylate compositions incorporating organic micropulp | |
WO2014189938A1 (en) | Cyanoacrylate compositions | |
US7687561B1 (en) | Toughened cyanoacrylate compositions | |
WO2019081753A1 (en) | Toughened, low odor/low bloom cyanoacrylate compositions | |
US20200255706A1 (en) | Cyanoacrylate compositions | |
GB2577817A (en) | Cyanoacrylate compositions | |
US20230365836A1 (en) | Cyanoacrylate compositions | |
EP4172221A1 (en) | Cyanoacrylate compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880012773.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08726274 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2680574 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009552699 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2009/009639 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008726274 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20097020994 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: PI0808436 Country of ref document: BR Kind code of ref document: A2 Effective date: 20090908 |